CN112939778B - Coumarin compound ester derivatives, preparation method and application thereof - Google Patents

Coumarin compound ester derivatives, preparation method and application thereof Download PDF

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CN112939778B
CN112939778B CN202110138206.0A CN202110138206A CN112939778B CN 112939778 B CN112939778 B CN 112939778B CN 202110138206 A CN202110138206 A CN 202110138206A CN 112939778 B CN112939778 B CN 112939778B
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butenyl
methoxy
methyl
acid
compound
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CN112939778A (en
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徐晖
吕敏
李绍晨
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Northwest A&F University
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Abstract

The invention relates to esters of coumarinsDerivatives, preparation method and application thereof. The structural general formula (I) of the series of coumarin compound ester derivatives is shown in the specification, R 1 Is selected from hydrogen, and R 2 Selected from hydrogen; or R 1 Is selected from methoxy, and R 2 Selected from 3-methyl-2-butenyl; r 3 One selected from alkyl, substituted or unsubstituted phenyl, substituted or unsubstituted cinnamyl, unsubstituted naphthylethyl, unsubstituted pyridyl or ferrocenyl. Experiments show that: the insecticidal activity of part of compounds in the series of coumarin compound ester derivatives on armyworm is equivalent to that of commercial botanical pesticide toosendanin, even higher than that of toosendanin; part of the derivatives have better poisoning activity on tetranychus cinnabarinus, and the activity is obviously improved compared with that of a parent coumarin compound, so that the derivatives are expected to be used for preparing efficient, environment-friendly and low-toxicity botanical insecticide/acaricide.

Description

Coumarin compound ester derivatives, preparation method and application thereof
Technical Field
The invention relates to coumarin compound ester derivatives and application of the series of derivatives in preparation of botanical insecticide/acaricide.
Background
Coumarin (Coumarin, structure shown in formula III) can be used as lactone compound of o-hydroxy cinnamic acid. Widely present in higher plants of the Rutaceae (Rutaceae), Umbelliferae (Umbelliferae), Compositae (Asteraceae), Leguminosae (Leguminosae) and the like [ European Journal of Pharmacology,1996,298(2), 191-197; phytochemistry,2000,53(6), 689-. Wherein R of osthole 1 Is methoxy, R 2 Is 3-methyl-2-butenyl [ Pest Management Science,2020,76, 3560-.
Figure BDA0002927594940000011
The coumarin compound has various biological activities in the aspects of medicines and pesticides. In medicine, there are anticancer [ European Journal of Pharmacology,2020,874,172990; european Journal of Pharmacology,2020,881,173207 ], anti-HIV, anti-inflammatory [ phytomedine, 2019,58, 152864; life Science,2019,225,117-131 ], and the activities of antibiotics [ Infection, Genetics and Evolution,2017,54, 1-3 ]. In the field of pesticides, there are antibacterial [ Industrial Crops and Products,2019,142,1118552 ], insecticidal [ Chinese Journal of Chemistry,2015,33(12), 1353-; pest Management Science,2012,68(7),1041-1047 ], antiviral [ Molecules,2019,25(1),65 ] and the like.
Disclosure of Invention
Based on the new research findings of the inventor, one of the purposes of the invention is to provide a class of coumarin compound ester derivatives.
Therefore, the chemical structural formula of the coumarin compound ester derivative provided by the invention is shown as the formula (I):
Figure BDA0002927594940000012
wherein:
R 1 is selected from hydrogen, and R 2 Selected from hydrogen; or R 1 Is selected from methoxy, and R 2 Selected from 3-methyl-2-butenyl;
R 3 selected from alkyl, substituted or unsubstituted phenyl, substituted or unsubstituted cinnamyl, unsubstituted naphthylethyl, unsubstituted pyridyl or ferrocenyl.
Optionally, the structure of the compound of formula (I) is one of the following structures:
(1):R 1 ＝R 2 ＝H；R 3 ＝-CH 2 CH 2 CH 3 ；
(2):R 1 ＝R 2 ＝H；R 3 ＝-CH 2 (CH 2 ) 8 CH 3 ；
(3):R 1 ＝R 2 ＝H；R 3 ＝-CH 2 (CH 2 ) 9 CH 3 ；
(4):R 1 ＝R 2 ＝H；R 3 ＝-CH 2 (CH 2 ) 11 CH 3 ；
(5):R 1 methoxy; r 2 2-butenyl-3-methyl; r 3 ＝-CH 3 ；
(6):R 1 Methoxy; r 2 2-butenyl-3-methyl; r 3 ＝-CH 2 CH 3 ；
(7):R 1 Methoxy; r 2 2-butenyl-3-methyl; r 3 ＝-CH 2 CH 2 CH 3 ；
(8):R 1 Methoxy; r 2 2-butenyl-3-methyl; r 3 ＝-CH 2 (CH 2 ) 8 CH 3 ；
(9):R 1 (ii) methoxy; r 2 2-butenyl-3-methyl; r 3 ＝-CH 2 (CH 2 ) 9 CH 3 ；
(10):R 1 Methoxy; r 2 2-butenyl-3-methyl; r 3 ＝-CH 2 (CH 2 ) 11 CH 3 ；
(11):R 1 (ii) methoxy; r 2 2-butenyl-3-methyl; r 3 A phenyl group;
(12):R 1 methoxy; r 2 2-butenyl-3-methyl; r 3 Meta-fluorophenyl;
(13):R 1 methoxy; r 2 2-butenyl-3-methyl; r 3 Para-fluorophenyl;
(14):R 1 methoxy; r 2 2-butenyl-3-methyl; r 3 O-chlorophenyl;
(15):R 1 methoxy; r is 2 2-butenyl-3-methyl; r 3 Meta-chlorophenyl;
(16):R 1 methoxy; r 2 2-butenyl-3-methyl; r 3 Para-chlorophenyl;
(17):R 1 methoxy; r 2 2-butenyl-3-methyl; r 3 Para-bromophenyl;
(18):R 1 methoxy; r 2 2-butenyl-3-methyl; r 3 Meta-trifluoromethylphenyl;
(19):R 1 methoxy; r 2 2-butenyl-3-methyl; r 3 Para-trifluoromethylphenyl;
(20):R 1 methoxy; r 2 2-butenyl-3-methyl; r 3 O-methoxyphenyl;
(21):R 1 methoxy; r 2 2-butenyl-3-methyl; r is 3 Meta-methoxyphenyl;
(22):R 1 methoxy; r 2 2-butenyl-3-methyl; r 3 Para-methoxyphenyl;
(23):R 1 methoxy; r 2 2-butenyl-3-methyl; r 3 Para-methylphenyl;
(24):R 1 methoxy; r 2 2-butenyl-3-methyl; r 3 α -naphthylethyl;
(25):R 1 methoxy; r is 2 2-butenyl-3-methyl; r 3 Cinnamyl;
(26):R 1 methoxy; r 2 2-butenyl-3-methyl; r is 3 3,4- (methylenedioxy) phenyl;
(27):R 1 methoxy; r 2 2-butenyl-3-methyl; r 3 3,4- (methylenedioxy) cinnamyl;
(28):R 1 methoxy; r 2 2-butenyl-3-methyl; r 3 (ii) 3,4- (ethylenedioxy) phenyl;
(29):R 1 methoxy; r 2 2-butenyl-3-methyl; r 3 3,4- (ethylenedioxy) cinnamyl;
(30):R 1 methoxy; r 2 2-butenyl-3-methyl; r 3 -3-pyridyl;
(31):R 1 methoxy; r is 2 2-butenyl-3-methyl; r 3 4-pyridyl;
(32):R 1 methoxy; r 2 2-butenyl-3-methyl; r 3 Ferrocenyl.
The invention also aims to provide a preparation method of the coumarin compound. Therefore, the preparation method provided by the invention comprises the following steps:
step 1, reacting a coumarin compound with an infrared aluminum solution to prepare an intermediate, wherein the structural formula of the coumarin compound is shown as a formula (II):
Figure BDA0002927594940000031
wherein R is 1 Is selected from hydrogen, and R 2 Selected from hydrogen; or R 1 Is selected from methoxy, and R 2 Selected from 3-methyl-2-butenyl;
step 2, intermediate and R 3 COOH to obtain the compound shown as the formula (I), wherein R 3 Selected from alkyl, substituted or unsubstituted phenyl, substituted or unsubstituted cinnamyl, unsubstituted naphthylethyl, unsubstituted pyridyl or ferrocenyl.
Optionally, the reaction in the step (1) is carried out in a tetrahydrofuran solution, nitrogen protection is provided, and the reaction temperature is-78-10 ℃.
Optionally, the R is 3 COOH is selected from one of acetic acid, propionic acid, butyric acid, undecanoic acid, lauric acid, tetradecanoic acid, benzoic acid, m-fluorobenzoic acid, p-fluorobenzoic acid, o-chlorobenzoic acid, m-chlorobenzoic acid, p-bromobenzoic acid, m-trifluoromethylbenzoic acid, p-trifluoromethylbenzoic acid, o-methoxybenzoic acid, m-methoxybenzoic acid, p-methylbenzoic acid, alpha naphthylacetic acid, piperic acid, 3,4- (methylenedioxy) cinnamic acid, 2, 3-dihydro-1, 4-benzodioxane-6-carboxylic acid, 1, 4-benzodioxane-6-acrylic acid, nicotinic acid, isonicotinic acid and ferrocenecarboxylic acid.
Optionally, the reaction in the step (2) is carried out in anhydrous dichloromethane, and EDC and DMAP are added simultaneously, wherein the reaction temperature is 20-30 ℃.
The coumarin compound ester derivative is applied to preparing pesticides. The coumarin compound ester derivative is applied to preparing acaricide. The pests comprise lepidoptera pests commonly seen in agriculture, such as three-year-old early armyworm and diamondback moth. The mite refers to mites which are commonly seen in agriculture, such as tetranychus cinnabarinus, tetranychus urticae koch and the like.
Drawings
FIG. 1 is a NMR spectrum of Compound 3;
FIG. 2 is a NMR carbon spectrum of Compound 3;
FIG. 3 is a NMR spectrum of Compound 9;
FIG. 4 is a NMR carbon spectrum of Compound 9;
FIG. 5 is a NMR spectrum of Compound 19;
FIG. 6 is a NMR carbon spectrum of Compound 19;
the invention is explained in further detail below by means of the figures and examples given by the inventors.
Detailed Description
Unless otherwise specified, the terminology herein is to be understood in light of the knowledge of one of ordinary skill in the relevant art.
The coumarin compound ester derivatives comprise coumarin ester derivatives and osthole ester derivatives. The synthetic route of the derivative of the invention is as follows:
Figure BDA0002927594940000041
according to the above synthetic route:
firstly, dissolving a proper amount of coumarin compounds (a, b) in a proper solvent (such as tetrahydrofuran), adding an aluminum red solution under proper conditions (such as nitrogen protection, -78-10 ℃) to react to prepare intermediates (c, d);
appropriate amount of intermediate and organic acid R 3 COOH is reacted in a suitable reaction system (such as a reaction system in which 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (EDC), 4-Dimethylaminopyridine (DMAP) and anhydrous dichloromethane are present) and under reaction conditions (such as a reaction temperature of 20-30 ℃) to produce the compound of the present invention.
The R is 3 COOH is selected from acetic acid, propionic acid, butyric acid, undecanoic acid, lauric acid, tetradecanoic acid, benzoic acid, m-fluorobenzoic acid, p-fluorobenzoic acid, o-chlorobenzoic acid, m-chlorobenzoic acid, p-bromobenzoic acid, m-trifluoromethylbenzoic acid, p-tris (trifluoromethyl) benzoic acidOne of fluoromethylbenzoic acid, o-methoxybenzoic acid, m-methoxybenzoic acid, p-methylbenzoic acid, alpha-naphthylacetic acid, piperic acid, 3,4- (methylenedioxy) cinnamic acid, 2, 3-dihydro-1, 4-benzodioxane-6-carboxylic acid, 1, 4-benzodioxane-6-acrylic acid, nicotinic acid, isonicotinic acid and ferrocenecarboxylic acid.
Example 1: preparation of coumarin compound ester derivative 1-32 compound
A method for preparing compound 3:
weighing 2mmol of coumarin (a), dissolving in 10mL of dry tetrahydrofuran, placing in an ice salt bath (-15 ℃) under the protection of nitrogen, dropwise adding 6mmol of red aluminum solution, continuing stirring for 1h, and detecting by TLC; after the reaction is completed, sequentially adding 2mL of methanol and 10mL of saturated NH4Cl aqueous solution to quench the reaction, adding ethyl acetate (20mL multiplied by 3), combining organic phases, drying, concentrating, and performing column chromatography separation to obtain an intermediate c with the yield of 34%;
intermediate c (0.2mmol), lauric acid (0.48mmol), 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (EDC,0.48mmol) and 4-dimethylaminopyridine (DMAP,0.04mmol) in 5mL dry dichloromethane were stirred at room temperature for 16 h; after completion of the reaction, 30mL of ethyl acetate was added to dilute the reaction mixture, and 15mL of a 0.1M aqueous hydrochloric acid solution, a 5% aqueous sodium bicarbonate solution and a saturated saline solution were sequentially added thereto to wash the mixture, and the organic phase was concentrated by drying and separated by thin layer chromatography to obtain Compound 3(53.5mg of a pale yellow liquid, yield 52%).
A method for preparing compound 9:
weighing 2mmol of osthole (b), dissolving in 10mL of dry tetrahydrofuran, placing in a reactor at-78 ℃ under the protection of nitrogen, dropwise adding 6mmol of red aluminum solution, continuously stirring for 24h, and detecting by TLC; after the reaction is completed, sequentially adding 2mL of methanol and 10mL of saturated NH4Cl aqueous solution to quench the reaction, adding ethyl acetate (20mL multiplied by 3), combining organic phases, drying, concentrating, and performing column chromatography separation to obtain an intermediate d with the yield of 36%;
unlike the preparation of compound 3, this compound 9 was prepared by stirring intermediate d (0.2mmol) with lauric acid (0.48mmol), EDC (0.48mmol) and DMAP (0.04mmol) in 5mL of anhydrous dichloromethane at room temperature for 18 h; after-treatment of compound 3, compound 9 was isolated by thin layer chromatography (41.7mg of a pale yellow liquid, yield 34%).
A method of preparing compound 19:
unlike the preparation of compound 3, this compound 19 was prepared by stirring intermediate d (0.2mmol) with p-trifluoromethylbenzoic acid (0.48mmol), EDC (0.48mmol) and DMAP (0.04mmol) in 5mL dry dichloromethane at room temperature for 10 h. After-treatment of compound 3, compound 19 was isolated by thin layer chromatography (55.6mg of a pale yellow solid, 47% yield).
The preparation method of the compounds 1, 2, 4-8, 10-18 and 20-32 comprises the following steps:
following the preparative route of the present invention, compounds 1, 2, 4-8, 10-18, 20-32 were prepared using appropriate preparative conditions with reference to the preparative procedures for compounds 3, 9 and 19 described above. The specific preparation method is available to the skilled in the art within the scope of the disclosure of the invention, and is not described herein.
The compounds 1 to 32 prepared by the above preparation methods have the following general formulae, and correspond to compounds having the structures (1) to (32):
Figure BDA0002927594940000061
(1):R 1 ＝H；R 2 ＝H；R 3 ＝-CH 2 CH 2 CH 3 ；
(2):R 1 ＝H；R 2 ＝H；R 3 ＝-CH 2 (CH 2 ) 8 CH 3 ；
(3):R 1 ＝H；R 2 ＝H；R 3 ＝-CH 2 (CH 2 ) 9 CH 3 ；
(4):R 1 ＝H；R 2 ＝H；R 3 ＝-CH 2 (CH 2 ) 11 CH 3 ；
(5):R 1 (ii) methoxy; r 2 2-butenyl-3-methyl; r 3 ＝-CH 3 ；
(6):R 1 (ii) methoxy; r 2 2-butenyl-3-methyl; r 3 ＝-CH 2 CH 3 ；
(7):R 1 Methoxy; r 2 2-butenyl-3-methyl; r 3 ＝-CH 2 CH 2 CH 3 ；
(8):R 1 Methoxy; r 2 2-butenyl-3-methyl; r 3 ＝-CH 2 (CH 2 ) 8 CH 3 ；
(9):R 1 Methoxy; r 2 2-butenyl-3-methyl; r 3 ＝-CH 2 (CH 2 ) 9 CH 3 ；
(10):R 1 Methoxy; r 2 2-butenyl-3-methyl; r 3 ＝-CH 2 (CH 2 ) 11 CH 3 ；
(11):R 1 Methoxy; r 2 2-butenyl-3-methyl; r 3 A phenyl group;
(12):R 1 methoxy; r 2 2-butenyl-3-methyl; r 3 -m-fluorophenyl;
(13):R 1 (ii) methoxy; r 2 2-butenyl-3-methyl; r 3 Para-fluorophenyl;
(14):R 1 methoxy; r 2 2-butenyl-3-methyl; r is 3 O-chlorophenyl;
(15):R 1 methoxy; r 2 2-butenyl-3-methyl; r 3 Meta-chlorophenyl;
(16):R 1 methoxy; r 2 2-butenyl-3-methyl; r 3 Para-chlorophenyl;
(17):R 1 methoxy; r 2 2-butenyl-3-methyl; r 3 Para-bromophenyl;
(18):R 1 methoxy; r 2 2-butenyl-3-methyl; r 3 Meta-trifluoromethylphenyl;
(19):R 1 (ii) methoxy; r is 2 2-butenyl-3-methyl; r 3 Para-trifluoromethylA phenyl group;
(20):R 1 methoxy; r 2 2-butenyl-3-methyl; r 3 O-methoxyphenyl;
(21):R 1 methoxy; r 2 2-butenyl-3-methyl; r 3 Meta-methoxyphenyl;
(22):R 1 methoxy; r 2 2-butenyl-3-methyl; r 3 Para-methoxyphenyl;
(23):R 1 methoxy; r 2 2-butenyl-3-methyl; r 3 Para-methylphenyl;
(24):R 1 (ii) methoxy; r 2 2-butenyl-3-methyl; r 3 α -naphthylethyl;
(25):R 1 methoxy; r 2 2-butenyl-3-methyl; r 3 Cinnamyl;
(26):R 1 methoxy; r 2 2-butenyl-3-methyl; r 3 3,4- (methylenedioxy) phenyl;
(27):R 1 methoxy; r 2 2-butenyl-3-methyl; r 3 3,4- (methylenedioxy) cinnamyl;
(28):R 1 methoxy; r 2 2-butenyl-3-methyl; r 3 (ii) 3,4- (ethylenedioxy) phenyl; (ii) a
(29):R 1 Methoxy; r 2 2-butenyl-3-methyl; r 3 3,4- (ethylenedioxy) cinnamyl;
(30):R 1 methoxy; r 2 2-butenyl-3-methyl; r 3 -3-pyridyl;
(31):R 1 methoxy; r 2 2-butenyl-3-methyl; r is 3 4-pyridyl;
(32):R 1 methoxy; r 2 2-butenyl-3-methyl; r 3 Ferrocenyl.
The physicochemical properties of compound 1 are as follows:
1) light yellow liquid, yield 76%;
2) the infrared spectrogram, nuclear magnetic resonance spectrogram and high-resolution mass spectrum of the compound are characterized in that:
IR cm -1 (KBr):2965,1743,1606,1174,1096； 1 H NMR(500MHz,CDCl 3 )δ:7.29-7.32(m,1H,Ar-H),7.20-7.25(m,2H,Ar-H),7.05(d,J＝8.0Hz,1H,Ar-H),6.53(d,J＝11.5Hz,1H,H-4),5.84-5.89(m,1H,H-3),4.69(dd,J＝1.0,6.5Hz,2H,H-2),2.51(t,J＝7.5Hz,2H,-COCH 2 -),2.27(t,J＝7.5Hz,2H,-COCH 2 -),1.73-1.81(m,2H,-CH 2 CH 3 ),1.62-1.69(m,2H-CH 2 CH 3 ),1.02(t,J＝7.5Hz,3H,-CH 2 CH 3 ),0.93(t,J＝7.5Hz,3H,-CH 2 CH 3 )； 13 C NMR(100MHz,CDCl 3 )δ:173.45,171.68,148.40,130.09,128.98,128.91,127.83,127.61,125.84,122.42,61.21,36.12,36.06,18.46,18.43,13.69；HRMS[ESI]:calcd for C 17 H 22 O 4 Na([M+Na] + ),313.1410；found,313.1403.
the physicochemical properties of compound 2 are as follows:
1) light yellow liquid, yield 62%;
2) the infrared spectrogram, nuclear magnetic resonance spectrogram and high-resolution mass spectrum of the compound are characterized in that:
IR cm -1 (KBr):2925,2857,1746,1455,1267,1105； 1 H NMR(500MHz,CDCl 3 )δ:7.28-7.31(m,1H,Ar-H),7.19-7.25(m,2H,Ar-H),7.05(d,J＝7.5Hz,1H,Ar-H),6.53(d,J＝11.5Hz,1H,H-4),5.83-5.88(m,1H,H-3),4.69-4.70(m,2H,H-2),2.51(t,J＝7.5Hz,2H,-COCH 2 CH 2 -),2.28(t,J＝7.5Hz,2H,-COCH 2 CH 2 -),1.70-1.76(m,2H,-COCH 2 CH 2 -),1.59-1.64(m,2H,-COCH 2 CH 2 -),1.25-1.43(m,28H,-2[(CH 2 ) 7 CH 3 ]),0.86-0.89(m,6H,-2[(CH 2 ) 7 CH 3 ])； 13 C NMR(100MHz,CDCl 3 )δ:173.60,171.83,148.42,130.09,128.98,128.89,127.83,127.60,125.82,122.42,61.23,34.27,34.22,31.91,29.58,29.57,29.50,29.48,29.33,29.28,29.16,29.15,24.96,22.70,14.13.HRMS[ESI]:calcd for C 31 H 50 O 4 Na([M+Na] + ),509.3601；found,509.3603.
the physicochemical properties of compound 3 are as follows:
1) light yellow liquid, yield 52%;
2) the infrared spectrogram, nuclear magnetic resonance spectrogram and high-resolution mass spectrum of the compound are characterized in that:
IR cm -1 (KBr):2924,2856,1748,1170,1106； 1 H NMR(500MHz,CDCl 3 )δ:7.29-7.32(m,1H,Ar-H),7.20-7.24(m,2H,Ar-H),7.05(d,J＝8.0Hz,1H,Ar-H),6.53(d,J＝11.5Hz,1H,H-4),5.84-5.89(m,1H,H-3),4.69(dd,J＝1.0,7.0Hz,2H,H-2),2.52(t,J＝7.5Hz,2H,-COCH 2 CH 2 -),2.29(t,J＝7.5Hz,2H,-COCH 2 CH 2 -),1.70-1.76(m,2H,-COCH 2 CH 2 -),1.59-1.65(m,2H-COCH 2 CH 2 -),1.25-1.41(m,32H,-2[(CH 2 ) 8 CH 3 ]),0.86-0.89(m,6H,-2[(CH 2 ) 8 CH 3 )； 13 C NMR(100MHz,CDCl 3 )δ:173.63,171.86,148.42,130.09,128.97,128.89,127.82,127.60,125.83,122.42,61.24,34.27,34.23,31.92,29.62,29.50,29.48,29.36,29.29,29.16,29.15,24.96,22.70,14.14；HRMS[ESI]:calcd for C 33 H 54 O 4 Na([M+Na] + ),537.3914；found,537.3903.
the physicochemical properties of compound 4 are as follows:
1) white solid, melting point 34-35 deg.C, yield 62%;
2) the infrared spectrogram and the nuclear magnetic resonance spectrogram of the compound are as follows:
IR cm -1 (KBr):2920,2852,1741,1609,1266,1093； 1 H NMR(400MHz,CDCl 3 )δ:7.29-7.33(m,1H,Ar-H),7.20-7.23(m,2H,Ar-H),7.05(d,J＝8.0Hz,1H,Ar-H),6.53(d,J＝11.6Hz,1H,H-4),5.83-5.89(m,1H,H-3),4.69(d,J＝6.4Hz,2H,H-2),2.52(t,J＝7.6Hz,2H,-COCH 2 CH 2 -),2.28(t,J＝7.6Hz,2H,-COCH 2 CH 2 -),1.70-1.77(m,2H,-COCH 2 CH 2 -),1.60-1.63(m,2H,-COCH 2 CH 2 -),1.25-1.40(m,40H,-2[(CH 2 ) 10 CH 3 ]),0.86-0.89(m,6H,-2[(CH 2 ) 10 CH 3 ])； 13 C NMR(100MHz,CDCl 3 )δ:173.63,171.86,148.43,130.10,128.99,128.89,127.83,127.62,125.83,122.42,61.24,34.28,34.24,31.94,29.70,29.67,29.62,29.51,29.48,29.37,29.29,29.17,29.15,24.97,22.71,14.14.
the physicochemical properties of compound 5 are as follows:
1) light yellow liquid, yield 76%;
2) the infrared spectrogram, nuclear magnetic resonance spectrogram and high-resolution mass spectrum of the compound are characterized in that:
IR cm -1 (KBr):2925,1741,1609,1223,1081； 1 H NMR(500MHz,CDCl 3 )δ:7.03(d,J＝8.5Hz,1H,H-5),6.74(d,J＝8.5Hz,1H,H-6),6.43(d,J＝11.5Hz,1H,H-4),5.76-5.81(m,1H,H-3),5.07(t,J＝7.0Hz,1H,H-2′),4.69(dd,J＝0.5,6.5Hz,2H,H-2),3.83(s,3H,-OCH 3 ),3.22(d,J＝6.0Hz,2H,H-1′),2.27(s,3H,-COCH 3 ),2.06(s,3H,-COCH 3 ),1.73(s,3H,-CH 3 ),1.66(s,3H,-CH 3 )； 13 C NMR(100MHz,CDCl 3 )δ:170.90,168.80,157.96,147.50,131.82,128.01,127.64,126.42,122.97,121.79,121.63,108.04,61.61,55.81,25.72,23.39,21.00,20.64,17.78；HRMS[ESI]:calcd for C 19 H 24 O 5 Na([M+Na] + ),355.1521；found,355.1514.
the physicochemical properties of compound 6 are as follows:
1) light yellow liquid, yield 60%;
2) the infrared spectrogram, nuclear magnetic resonance spectrogram and high-resolution mass spectrum of the compound are characterized in that:
IR cm -1 (KBr):2979,2932,1744,1609,1270,1082； 1 H NMR(500MHz,CDCl 3 )δ:7.04(d,J＝8.5Hz,1H,H-5),6.74(d,J＝8.5Hz,1H,H-6),6.41(d,J＝11.5Hz,1H,H-4),5.75-5.80(m,1H,H-3),5.06-5.09(m,1H,H-2′),4.69-4.71(m,2H,H-2),3.83(s,3H,-OCH 3 ),3.21(d,J＝6.0Hz,2H,H-1′),2.54(q,J＝7.5Hz,2H,-COCH 2 -),2.31(q,J＝7.5Hz,2H,-COCH 2 -),1.72(s,3H,-CH＝C(CH 3 ) 2 ),1.65(s,3H,-CH＝C(CH 3 ) 2 ),1.24(t,J＝7.5Hz,3H,-CH 2 CH 3 ),1.12(t,J＝7.5Hz,3H,-CH 2 CH 3 )； 13 C NMR(100MHz,CDCl 3 )δ:174.32,172.17,157.94,147.54,131.78,128.01,127.60,126.48,123.02,121.88,121.73,107.95,61.47,55.80,27.56,27.46,25.71,23.34,17.77,9.20,9.13.HRMS[ESI]:calcd for C 21 H 28 O 5 Na([M+Na] + ),383.1834；found,383.1830.
the physicochemical properties of compound 7 are as follows:
1) light yellow liquid, yield 46%;
2) the infrared spectrogram, nuclear magnetic resonance spectrogram and high-resolution mass spectrum of the compound are characterized in that:
IR cm -1 (KBr):2966,1739,1610,1267,1088； 1 H NMR(500MHz,CDCl 3 )δ:7.04(d,J＝8.5Hz,1H,H-5),6.73(d,J＝8.0Hz,1H,H-6),6.42(d,J＝11.5Hz,1H,H-4),5.74-5.79(m,1H,H-3),5.06-5.09(m,1H,H-2′),4.69(d,J＝6.5Hz,2H,H-2),3.82(s,3H,-OCH 3 ),3.21(d,J＝4.5Hz,2H,H-1′),2.50(t,J＝7.5Hz,2H,-COCH 2 -),2.28(t,J＝7.5Hz,2H,-COCH 2 -),1.62-1.79(m,10H,-CH 2 CH 3 and-CH＝C(CH 3 ) 2 ),1.01(t,J＝7.5Hz,3H,-CH 2 CH 3 ),0.93(t,J＝7.5Hz,3H,-CH 2 CH 3 )； 13 C NMR(100MHz,CDCl 3 )δ:173.50,171.37,157.95,147.57,131.80,128.13,127.60,126.51,123.04,121.90,121.76,107.93,61.37,55.79,36.17,35.91,25.71,23.37,18.46,18.42,17.80,13.79,13.69；HRMS[ESI]:calcd for C 23 H 32 O 5 Na([M+Na] + ),411.2147；found,411.2136.
the physicochemical properties of compound 8 are as follows:
1) light yellow liquid, yield 29%;
2) the infrared spectrogram, nuclear magnetic resonance spectrogram and high-resolution mass spectrum of the compound are characterized in that:
IR cm -1 (KBr):2925,2856，1741,1606,1268,1094； 1 H NMR(500MHz,CDCl 3 )δ:7.04(d,J＝8.5Hz,1H,H-5),6.73(d,J＝8.5Hz,1H,H-6),6.41(d,J＝11.5Hz,1H,H-4),5.74-5.79(m,1H,H-3),5.06(t,J＝6.0Hz,1H,H-2′),4.68(d,J＝6.5Hz,2H,H-2),3.83(s,3H,-OCH 3 ),3.20(s,2H,H-1′),2.51(t,J＝7.5Hz,2H,-COCH 2 CH 2 -),2.28(t,J＝7.5Hz,2H,-COCH 2 CH 2 -),1.70-1.76(m,5H,-COCH 2 CH 2 -and-CH＝C(CH 3 ) 2 ),1.60-1.65(m,5H,-COCH 2 CH 2 -and-CH＝C(CH 3 ) 2 ),1.25-1.41(m,28H,-2[(CH 2 ) 7 CH 3 ]),0.86-0.89(m,6H,-2[(CH 2 ) 7 CH 3 ])； 13 C NMR(100MHz,CDCl 3 )δ:173.70,171.56,157.94,147.57,131.79,128.11,127.60,126.47,123.03,121.89,121.76,107.92,61.39,55.78,34.32,34.07,31.90,29.58,29.49,29.33,29.31,29.28,29.24,29.17,25.72,24.98,24.93,23.36,22.69,17.82,14.13；HRMS[ESI]:calcd for C 37 H 60 O 5 Na([M+Na] + ),607.4333；found,607.4330.
the physicochemical properties of compound 9 are as follows:
1) yellowish liquid, yield 34%;
2) the infrared spectrogram, nuclear magnetic resonance spectrogram and high-resolution mass spectrum of the compound are characterized in that:
IR cm -1 (KBr):2924,2855,1742,1610,1268,1091； 1 H NMR(500MHz,CDCl 3 )δ:7.04(d,J＝8.5Hz,1H,H-5),6.73(d,J＝8.5Hz,1H,H-6),6.41(d,J＝11.5Hz,1H,H-4),5.74-5.79(m,1H,H-3),5.06(t,J＝7.0Hz,1H,H-2′),4.68(d,J＝6.5Hz,2H,H-2),3.82(s,3H,-OCH 3 ),3.20(d,J＝5.5Hz,2H,H-1′),2.51(t,J＝7.5Hz,2H,-COCH 2 -),2.28(t,J＝8.0Hz,2H,-COCH 2 -),1.70-1.76(m,5H,-CH 2 CH 3 and-CH＝C(CH 3 ) 2 ),1.58-1.65(m,5H,-CH 2 CH 3 and-CH＝C(CH 3 ) 2 ),1.25-1.41(m,32H,-CH 2 -),0.86-0.89(m,6H,-CH 2 CH 3 )； 13 C NMR(100MHz,CDCl 3 )δ:173.68,171.53,157.97,147.61,131.76,128.14,127.60,126.50,123.08,121.93,121.80,107.94,63.71,61.40,55.79,34.34,34.08,31.93,29.63,29.50,29.49,29.35,29.31,29.29,29.25,29.18,25.71,25.37,25.00,24.97,24.94,23.38,22.70,17.81,14.13；HRMS[ESI]:calcd for C39H64O5Na([M+Na]+),635.4651；found,635.4641.
the physicochemical properties of compound 10 are as follows:
1) light yellow solid, melting point 34-35 deg.C, yield 59%;
2) the infrared spectrogram and nuclear magnetic resonance spectrogram of the compound are characterized in that:
IR cm -1 (KBr):2923,2854,1741,1606,1267,1089； 1 H NMR(400MHz,CDCl 3 )δ:7.03(d,J＝8.4Hz,1H,H-5),6.73(d,J＝8.4Hz,1H,H-6),6.41(d,J＝11.2Hz,1H,H-4),5.73-5.79(m,1H,H-3),5.07(s,1H,H-2′),4.68(d,J＝6.0Hz,2H,H-2),3.83(s,3H,-OCH 3 ),3.20(s,2H,H-1′),2.51(t,J＝7.6Hz,2H,-COCH 2 CH 2 -),2.29-2.32(m,2H,-COCH 2 CH 2 -),1.63-1.72(m,10H,-COCH 2 CH 2 -and-CH＝C(CH 3 ) 2 ),1.25-1.39(m,40H,-2[(CH 2 ) 10 CH 3 ]),0.86-0.89(m,6H)； 13 C NMR(100MHz,CDCl 3 )δ:173.69,171.55,157.95,147.58,131.78,128.12,127.59,126.48,123.06,121.91,121.77,107.93,61.39,55.79,34.33,34.07,31.93,29.69,29.66,29.62,29.49,29.37,29.30,29.24,29.17,25.71,24.99,24.93,23.37,22.70,17.81,14.13.
the physicochemical properties of compound 11 are as follows:
1) colorless liquid, yield 46%;
2) the infrared spectrogram, nuclear magnetic resonance spectrogram and high-resolution mass spectrum of the compound are characterized in that:
IR cm -1 (KBr):2923,1730,1609,1269,1090； 1 H NMR(500MHz,CDCl 3 )δ:8.19(d,J＝8.0Hz,2H,Ar-H),8.01(d,J＝7.5Hz,2H,Ar-H),7.61(t,J＝7.0Hz,1H,Ar-H),7.53(t,J＝7.5Hz,1H,Ar-H),7.48(t,J＝7.5Hz,2H,Ar-H),7.40(t,J＝7.5Hz,2H,Ar-H),7.17(d,J＝8.5Hz,1H,H-5),6.81(d,J＝8.5Hz,1H,H-6),6.53(d,J＝11.5Hz,1H,H-4),5.82-5.87(m,1H,H-3),5.10(t,J＝7.0Hz,1H,H-2′),4.98(d,J＝6.5Hz,2H,H-2),3.86(s,3H,-OCH 3 ),3.28(s,2H,H-1′),1.57(s,3H,-CH 3 ),1.50(s,3H,-CH 3 )； 13 C NMR(100MHz,CDCl 3 )δ:166.43,164.43,158.04,147.83,133.58,132.91,131.85,130.22,130.19,129.65,129.17,128.56,128.31,128.29,127.71,126.32,123.24,122.13,121.69,108.18,62.13,55.87,25.66,23.45,17.72；HRMS[ESI]:calcd for C 29 H 28 O 5 Na([M+Na] + ),479.1834；found,479.1825.
the physicochemical properties of compound 12 are as follows:
1) light yellow solid, melting point 59-61 deg.C, yield 58%;
2) the compound has the characteristics of infrared spectrogram, nuclear magnetic resonance spectrogram and high-resolution mass spectrum:
IR cm -1 (KBr):2918,1725,1603,1277,1195,1091； 1 H NMR(500MHz,CDCl 3 )δ:7.98(d,J＝8.0Hz,1H,Ar-H),7.85-7.87(m,1H,Ar-H),7.80(d,J＝8.0Hz,1H,Ar-H),7.67-7.70(m,1H,Ar-H),7.45-7.50(m,1H,Ar-H),7.37-7.42(m,1H,Ar-H),7.31-7.35(m,1H,Ar-H),7.23-7.26(m,1H,Ar-H),7.15(d,J＝8.5Hz,1H,H-5),6.82(d,J＝8.5Hz,1H,H-6),6.52(d,J＝11.0Hz,1H,H-4),5.82-5.87(m,1H,H-3),5.07(t,J＝6.5Hz,1H,H-2′),4.96(d,J＝6.5Hz,2H,H-2),3.87(s,3H,-OCH 3 ),3.27(s,2H,H-1′),1.57(s,3H,-CH 3 ),1.50(s,3H,-CH 3 )；HRMS[ESI]:calcd for C 29 H 26 F 2 O 5 Na([M+Na] + ),515.1646；found,515.1638.
the physicochemical properties of compound 13 are as follows:
1) light yellow liquid, yield 36%;
2) the infrared spectrogram, nuclear magnetic resonance spectrogram and high-resolution mass spectrum of the compound are characterized in that:
IR cm -1 (KBr):2923,1731,1604,1267,1092； 1 H NMR(500MHz,CDCl 3 )δ:8.19-8.22(m,2H,Ar-H),8.01-8.04(m,2H,Ar-H),7.15-7.18(m,3H,Ar-H and H-5),7.07(t,J＝8.5Hz,2H,Ar-H),6.81(d,J＝8.5Hz,1H,H-6),6.51(d,J＝11.5Hz,1H,H-4),5.81-5.86(m,1H,H-3),5.07(t,J＝7.0Hz,1H,H-2′),4.96(d,J＝6.5Hz,2H,H-2),3.86(s,3H,-OCH 3 ),3.27(s,2H,H-1′),1.57(s,3H,-CH 3 ),1.50(s,3H,-CH 3 )； 13 C NMR(100MHz,CDCl 3 )δ:165.45,164.89(d,J C-F ＝253.8Hz)164.49(d,J C-F ＝252.3Hz),163.44,158.06,147.68,132.75(d,J C-F ＝9.3Hz),132.13(d,J C-F ＝9.4Hz),131.88,128.27,127.71,126.38(d,J C-F ＝2.9Hz),126.26,125.38(d,J C-F ＝2.9Hz),123.22,122.04,121.65,115.57(d,J C-F ＝34.4Hz),115.36(d,J C-F ＝34.3Hz),108.24,62.21,55.87,25.65,23.43,17.73；HRMS[ESI]:calcd for C 29 H 26 F 2 O 5 Na([M+Na] + ),515.1646；found,515.1639
the physicochemical properties of compound 14 are as follows:
1) light yellow liquid, yield 46%;
2) the infrared spectrogram and nuclear magnetic resonance spectrogram of the compound are characterized in that:
IR cm -1 (KBr):2923,1733,1601,1282,1105,747； 1 H NMR(500MHz,CDCl 3 )δ:8.06(dd,J＝1.5,8.0Hz,1H,Ar-H),7.78(dd,J＝1.5,8.0Hz,1H,Ar-H),7.34-7.52(m,5H,Ar-H),7.27-7.30(m,1H,Ar-H),7.18(d,J＝8.5Hz,1H,H-5),6.81(d,J＝9.0Hz,1H,H-6),6.61(d,J＝11.5Hz,1H,H-4),5.90-5.95(m,1H,H-3),5.10(t,J＝7.0Hz,1H,H-2′),4.97(d,J＝7.0Hz,2H,H-2),3.86(s,3H,-OCH 3 ),3.32(s,2H,H-1′),1.61(s,3H,-CH 3 ),1.58(s,3H,-CH 3 )； 13 C NMR(100MHz,CDCl 3 )δ:165.50,163.12,158.14,147.55,134.61,133.72,133.24,132.50,132.06,132.01,131.47,131.44,131.02,130.09,128.80,127.81,126.69,126.55,126.25,123.27,121.90,121.63,108.31,62.57,55.89,25.69,23.44,17.73.
the physicochemical properties of compound 15 are as follows:
1) light yellow solid, melting point 71-73 deg.C, yield 43%;
2) the infrared spectrogram and nuclear magnetic resonance spectrogram of the compound are characterized in that:
IR cm -1 (KBr):2918,1728,1607,1248,1087,739； 1 H NMR(500MHz,CDCl 3 )δ:8.16(t,J＝1.5Hz,1H,Ar-H),8.06(d,J＝8.0Hz,1H,Ar-H),7.98(t,J＝2.0Hz,1H,Ar-H),7.89(d,J＝7.5Hz,1H,Ar-H),7.59-7.61(m,1H,Ar-H),7.51-7.53(m,1H,Ar-H),7.42(t,J＝8.0Hz,1H,Ar-H),7.35(t,J＝7.5Hz,1H,Ar-H),7.14(d,J＝8.5Hz,1H,H-5),6.82(d,J＝9.0Hz,1H,H-6),6.52(d,J＝11.5Hz,1H,H-4),5.82-5.87(m,1H,H-3),5.07(t,J＝7.0Hz,1H,H-2′),4.96(d,J＝7.0Hz,2H,H-2),3.86(s,3H,-OCH 3 ),3.27(s,2H,H-1′),1.58(s,3H,-CH 3 ),1.50(s,3H,-CH 3 )； 13 C NMR(100MHz,CDCl 3 )δ:165.20,163.25,158.08,147.60,134.78,134.47,133.66,132.97,132.00,131.89,130.88,130.19,129.92,129.70,129.66,128.43,128.27,127.79,127.75,126.22,123.17,121.92,121.61,108.34,62.41,55.89,25.64,23.41,17.75；HRMS[ESI]:calcd for C 29 H 26 Cl 2 O 5 Na([M+Na] + ),547.1055,549.1025,551.0996；found,547.1044,549.1012,551.0974.
the physicochemical properties of compound 16 are as follows:
1) light yellow liquid, yield 42%;
2) the infrared spectrogram, nuclear magnetic resonance spectrogram and high-resolution mass spectrum of the compound are characterized in that:
IR cm -1 (KBr):2923,1730,1601,1266,1091,681； 1 H NMR(500MHz,CDCl 3 )δ:8.11(d,J＝8.5Hz,2H,Ar-H),7.92(d,J＝8.5Hz,2H,Ar-H),7.46(d,J＝8.5Hz,2H,Ar-H),7.38(d,J＝8.5Hz,2H,Ar-H),7.14(d,J＝8.5Hz,1H,H-5),6.80(d,J＝8.5Hz,1H,H-6),6.50(d,J＝11.5Hz,1H,H-4),5.80-5.85(m,1H,H-3),5.07(t,J＝6.5Hz,1H,H-2′),4.95(d,J＝6.5Hz,2H,H-2),3.86(s,3H,-OCH 3 ),3.27(s,2H,H-1′),1.57(s,3H,-CH 3 ),1.50(s,3H,-CH 3 )； 13 C NMR(100MHz,CDCl 3 )δ:165.54,163.57,158.08,147.62,140.19,139.40,131.92,131.54,131.03,128.98,128.67,128.60,128.33,127.72,127.60,126.23,123.21,121.99,121.63,108.30,62.30,55.88,25.65,23.43,17.76；HRMS[ESI]:calcd for C 29 H 26 Cl 2 O 5 Na([M+Na] + ),547.1055,549.1025,551.0996；found,547.1052,549.1020,551.0975.
the physicochemical properties of compound 17 are as follows:
1) light yellow solid, melting point 79-81 deg.C, yield 51%;
2) the infrared spectrogram, nuclear magnetic resonance spectrogram and high-resolution mass spectrum of the compound are characterized in that:
IR cm -1 (KBr):2917,1728,1590,1265,1084,679； 1 H NMR(500MHz,CDCl 3 )δ:8.03(d,J＝8.5Hz,2H,Ar-H),7.84(d,J＝8.5Hz,2H,Ar-H),7.62(d,J＝8.5Hz,2H,Ar-H),7.54(d,J＝8.5Hz,2H,Ar-H),7.13(d,J＝8.5Hz,1H,H-5),6.80(d,J＝8.5Hz,1H,H-6),6.50(d,J＝11.5Hz,1H,H-4),5.80-5.85(m,1H,H-3),5.07(t,J＝7.0Hz,1H,H-2′),4.94(d,J＝6.5Hz,2H,H-2),3.86(s,3H,-OCH 3 ),3.26(s,2H,H-1′),1.57(s,3H,-CH 3 ),1.50(s,3H,-CH 3 )； 13 C NMR(100MHz,CDCl 3 )δ:165.67,163.71,158.07,147.59,131.97,131.93,131.67,131.64,131.16,129.04,128.89,128.34,128.08,128.04,127.72,126.21,123.19,121.96,121.61,108.30,62.32,55.88,25.65,23.42,17.77；HRMS[ESI]:calcd for C 29 H 26 Br 2 O 5 Na([M+Na] + ),635.0045,637.0024,639.0004；found,635.0034,637.0012,638.9991.
the physicochemical properties of compound 18 are as follows:
1) light yellow liquid, yield 40%;
2) the infrared spectrogram, nuclear magnetic resonance spectrogram and high-resolution mass spectrum of the compound are characterized in that:
IR cm -1 (KBr):2926,1735,1612,1335,1244,1080； 1 H NMR(500MHz,CDCl 3 )δ:8.45(s,1H,Ar-H),8.36(d,J＝7.5Hz,1H,Ar-H),8.28(s,1H,Ar-H),8.19(d,J＝8.0Hz,1H,Ar-H),7.88(d,J＝8.0Hz,1H,Ar-H),7.80(d,J＝8.0Hz,1H,Ar-H),7.63(t,J＝8.0Hz,1H,Ar-H),7.55(t,J＝8.0Hz,1H,Ar-H),7.16(d,J＝8.5Hz,1H,H-5),6.83(d,J＝8.5Hz,1H,H-6),6.54(d,J＝11.5Hz,1H,H-4),5.84-5.89(m,1H,H-3),5.07(t,J＝7.0Hz,1H,H-2′),5.01(d,J＝6.5Hz,2H,H-2),3.87(s,3H,-OCH 3 ),3.28(s,2H,H-1′),1.56(s,3H,-CH 3 ),1.48(s,3H,-CH 3 )；HRMS[ESI]:calcd for C 31 H 26 F 6 O 5 Na([M+Na] + ),615.1582；found,615.1565.
the physicochemical properties of compound 19 are as follows:
1) light yellow solid, melting point 74-76 deg.C, yield 47%;
2) the infrared spectrogram, nuclear magnetic resonance spectrogram and high-resolution mass spectrum of the compound are characterized in that:
IR cm -1 (KBr):2925,1731,1614,1325,1271,1076；IR cm -1 (KBr):2925,1731,1614,1325,1271,1076； 1 H NMR(500MHz,CDCl 3 )δ:8.29(d,J＝8.0Hz,2H,Ar-H),8.10(d,J＝8.0Hz,2H,Ar-H),7.75(d,J＝8.5Hz,2H,Ar-H),7.67(d,J＝8.0Hz,2H,Ar-H),7.15(d,J＝8.5Hz,1H,H-5),6.82(d,J＝9.0Hz,1H,H-6),6.53(d,J＝11.5Hz,1H,H-4),5.82-5.87(m,1H,H-3),5.07(t,J＝7.0Hz,1H,H-2′),4.99(d,J＝7.0Hz,2H,H-2),3.87(s,3H,-OCH 3 ),3.28(s,2H,H-1′),1.57(s,3H,-CH 3 ),1.49(s,3H,-CH 3 )； 13 C NMR(100MHz,CDCl 3 )δ:165.18,163.24,158.16,147.54,134.64(d,J C-F ＝62.8Hz),134.31(d,J C-F ＝62.7Hz),133.36,132.40,132.04,130.56,130.04,128.46,127.78,126.22,125.61(q,J C-F ＝3.8Hz),125.32(q,J C-F ＝3.7Hz),124.89(d,J C-F ＝9.1Hz),123.20,122.18(d,J C-F ＝9.2Hz),121.89,121.56,108.43,62.56,55.90,25.63,23.44,17.75；HRMS[ESI]:calcd for C 31 H 26 F 6 O 5 Na([M+Na] + ),615.1582；found,615.1567.
the physicochemical properties of compound 20 are as follows:
1) yellowish liquid, yield 49%;
2) the infrared spectrogram, nuclear magnetic resonance spectrogram and high-resolution mass spectrum of the compound are characterized in that:
IR cm -1 (KBr):2928,1727,1602,1246,1084； 1 H NMR(500MHz,CDCl 3 )δ:7.98(dd,J＝1.5,7.5Hz,1H,Ar-H),7.77-7.78(m,1H,Ar-H),7.51(t,J＝8.5Hz,1H,Ar-H),7.44(t,J＝9.0Hz,1H,Ar-H),7.21(d,J＝8.0Hz,1H,Ar-H),7.01-7.03(m,2H,Ar-H),6.94-6.97(m,2H,Ar-H),6.79(d,J＝8.5Hz,1H,H-6),6.60(d,J＝11.5Hz,1H,H-4),5.86-5.91(m,1H,H-3),5.14(t,J＝7.0Hz,1H,H-2′),4.95(d,J＝6.5Hz,2H,H-2),3.92(s,3H,-OCH 3 ),3.89(s,3H,-OCH 3 ),3.86(s,3H,-OCH 3 ),3.31(s,2H,H-1′),1.61(s,3H,-CH 3 ),1.58(s,3H,-CH 3 )；HRMS[ESI]:calcd for C 31 H 32 O 7 Na([M+Na] + ),539.2046；found,539.2038.
the physicochemical properties of compound 21 are as follows:
1) light yellow liquid, yield 34%;
2) the infrared spectrogram, nuclear magnetic resonance spectrogram and high-resolution mass spectrum of the compound are characterized in that:
IR cm -1 (KBr):2926,1727,1598,1277,1090； 1 H NMR(500MHz,CDCl 3 )δ:7.80(d,J＝7.5Hz,1H,Ar-H),7.69(s,1H,Ar-H),7.61(d,J＝7.5Hz,1H,Ar-H),7.54(s,1H,Ar-H),7.38(t,J＝7.5Hz,1H,Ar-H),7.31(t,J＝8.0Hz,1H,Ar-H),7.16-7.19(m,2H,Ar-H and H-5),7.08-7.10(m,1H,Ar-H),6.81(d,J＝8.5Hz,1H,H-6),6.53(d,J＝11.0Hz,1H,H-4),5.82-5.87(m,1H,H-3),5.10(t,J＝6.5Hz,1H,H-2′),4.97(d,J＝6.0Hz,2H,H-2),3.84-3.87(m,9H,-OCH 3 ),3.28(s,2H,H-1′),1.58(s,3H,-CH 3 ),1.52(s,3H,-CH 3 )；HRMS[ESI]:calcd for C 31 H 32 O 7 Na([M+Na] + ),539.2046；found,539.2033.
the physicochemical properties of compound 22 are as follows:
1) white solid with melting point 95-97 deg.c and yield 42%;
2) the infrared spectrogram, nuclear magnetic resonance spectrogram and high-resolution mass spectrum of the compound are characterized in that:
IR cm -1 (KBr):2925,1721,1607,1261,1091； 1 H NMR(500MHz,CDCl 3 )δ:8.14(d,J＝9.0Hz,2H,Ar-H),7.96(d,J＝9.0Hz,2H,Ar-H),7.16(d,J＝8.5Hz,1H,H-5),6.95(d,J＝9.0Hz,2H,Ar-H),6.88(d,J＝9.0Hz,2H,Ar-H),6.79(d,J＝8.5Hz,1H,H-6),6.51(d,J＝11.5Hz,1H,H-4),5.80-5.85(m,1H,H-3),5.10-5.13(m,1H,H-2′),4.94(d,J＝5.5Hz,2H,H-2),3.85-3.88(m,9H,-OCH 3 ),3.27(s,2H,H-1′),1.58(s,3H,-CH 3 ),1.52(s,3H,-CH 3 )； 13 C NMR(100MHz,CDCl 3 )δ:166.19,164.13,163.86,163.31,157.99,147.89,132.34,131.74,131.68,128.15,127.67,126.37,123.31,122.66,122.28,121.78,121.53,113.81,113.54,108.08,61.91,55.85,55.50,55.42,25.69,23.48,17.75；HRMS[ESI]:calcd for C 31 H 32 O 7 Na([M+Na] + ),539.2046；found,539.2042.
the physicochemical properties of compound 23 are as follows:
1) light yellow liquid, yield 45%;
2) the infrared spectrogram, nuclear magnetic resonance spectrogram and high-resolution mass spectrum of the compound are characterized in that:
IR cm -1 (KBr):2922,1728,1609,1266,1093； 1 H NMR(500MHz,CDCl 3 )δ:8.08(d,J＝8.0Hz,2H,Ar-H),7.90(d,J＝8.0Hz,2H,Ar-H),7.28(d,J＝8.0Hz,2H,Ar-H),7.21(d,J＝8.0Hz,2H,Ar-H),7.16(d,J＝8.5Hz,1H,H-5),6.80(d,J＝8.5Hz,1H,H-6),6.51(d,J＝11.5Hz,1H,H-4),5.80-5.85(m,1H,H-3),5.10(t,J＝7.0Hz,1H,H-2′),4.95(d,J＝6.0Hz,2H,H-2),3.86(s,3H,-OCH 3 ),3.27(s,2H,H-1′),2.44(s,3H,Ph-CH 3 ),2.40(s,3H,Ph-CH 3 ),1.58(s,3H,-CH 3 ),1.51(s,3H,-CH 3 )； 13 C NMR(100MHz,CDCl 3 )δ:166.51,164.48,158.00,147.86,144.39,143.54,131.78,130.28,129.68,129.27,129.02,128.19,127.68,127.47,126.42,126.34,123.27,122.19,121.74,108.11,61.99,55.85,25.68,23.46,21.77,21.67,17.75；HRMS[ESI]:calcd for C 31 H 32 O 5 Na([M+Na] + ),507.2147；found,507.2145.
the physicochemical properties of compound 24 are as follows:
1) light yellow liquid, yield 27%;
2) the infrared spectrogram and nuclear magnetic resonance spectrogram of the compound are characterized in that:
IR cm -1 (KBr):2920,1736 1605,1263,1077； 1 H NMR(500MHz,CDCl 3 )δ:8.05(d,J＝7.5Hz,1H,Ar-H),7.97(d,J＝8.0Hz,1H,Ar-H),7.82-7.86(m,2H,Ar-H),7.76-7.79(m,2H,Ar-H),7.40-7.53(m,8H,Ar-H),6.75(d,J＝8.5Hz,1H,H-5),6.48(d,J＝8.5Hz,1H,H-6),6.00(d,J＝11.5Hz,1H,H-4),5.30-5.35(m,1H,H-3),4.87(t,J＝7.5Hz,1H,H-2′),4.48(d,J＝6.5Hz,2H,H-2),4.22(s,2H,-COCH 2 -),4.03(s,2H,-COCH 2 -),3.74(s,3H,-OCH 3 ),3.07(s,2H,H-1′),1.62(s,3H,-CH 3 ),1.58(s,3H,-CH 3 ).
the physicochemical properties of compound 25 are as follows:
1) light yellow solid, melting point 62-64 deg.C, yield 24%;
2) the infrared spectrogram, nuclear magnetic resonance spectrogram and high-resolution mass spectrum of the compound are characterized in that:
IR cm -1 (KBr):2921,1721,1634,1132,1077； 1 H NMR(500MHz,CDCl 3 )δ:7.86(d,J＝16.0Hz,1H,-CH＝CH-),7.66(d,J＝16.0Hz,1H,-CH＝CH-),7.58(s,2H,Ar-H),7.50(s,2H,Ar-H),7.38-7.41(m,6H,Ar-H),7.13(d,J＝8.5Hz,1H,H-5),6.79(d,J＝8.0Hz,1H,H-6),6.63(d,J＝16.0Hz,1H,-CH＝CH-),6.52(d,J＝11.5Hz,1H,H-4),6.42(d,J＝16.0Hz,1H,-CH＝CH-),5.82-5.87(m,1H,H-3),5.12(t,J＝6.5Hz,1H,H-2′),4.87(d,J＝6.5Hz,2H,H-2),3.85(s,3H,-OCH 3 ),3.28(s,2H,H-1′),1.68(s,3H,-CH 3 ),1.64(s,3H,-CH 3 )；HRMS[ESI]:calcd for C 33 H 32 O 5 Na([M+Na] + ),531.2147；found,531.2137.
the physicochemical properties of compound 26 are as follows:
1) light yellow solid, melting point 83-85 deg.C, yield 27%;
2) the infrared spectrogram, nuclear magnetic resonance spectrogram and high-resolution mass spectrum of the compound are characterized in that:
IR cm -1 (KBr):2911,1720,1611,1266,1085； 1 H NMR(500MHz,CDCl 3 )δ:7.80(d,J＝8.0Hz,1H,Ar-H),7.60-7.63(m,2H,Ar-H),7.44(s,1H,Ar-H),7.14(d,J＝8.5Hz,1H,H-5),6.87(d,J＝8.0Hz,1H,H-6),6.79(t,J＝7.5Hz,2H,Ar-H),6.50(d,J＝11.5Hz,1H,H-4),6.06(s,2H,-OCH 2 O-),6.02(s,2H,-OCH 2 O-),5.80-5.85(m,1H,H-3),5.09(t,J＝7.0Hz,1H,H-2′),4.92(d,J＝6.0Hz,2H,H-2),3.85(s,3H,-OCH 3 ),3.26(s,2H,H-1′),1.59(s,3H,-CH 3 ),1.54(s,3H,-CH 3 )；HRMS[ESI]:calcd for C 31 H 28 O 9 Na([M+Na] + ),567.1631；found,567.1626.
the physicochemical properties of compound 27 are as follows:
1) light yellow solid, melting point 55-57 ℃, yield 27%;
2) the infrared spectrogram, nuclear magnetic resonance spectrogram and high-resolution mass spectrum of the compound are characterized in that:
IR cm -1 (KBr):2917,1713,1631,1251,1162； 1 H NMR(500MHz,CDCl 3 )δ:7.75(d,J＝15.5Hz,1H,-CH＝CH-),7.56(d,J＝16.0Hz,1H,-CH＝CH-),7.11(d,J＝8.5Hz,1H,H-5),7.05-7.08(m,2H,Ar-H),6.97-6.99(m,2H,Ar-H),6.78-6.83(m,3H,Ar-H and H-6),6.50(d,J＝11.5Hz,1H,H-4),6.44(d,J＝15.5Hz,1H,-CH＝CH-),6.23(d,J＝16.0Hz,1H,-CH＝CH-),6.00(d,J＝10.0Hz,4H,-OCH 2 O-),5.80-5.85(m,1H,H-3),5.11(t,J＝7.0Hz,1H,H-2′),4.84(d,J＝6.5Hz,2H,H-2),3.85(s,3H,-OCH 3 ),3.26(s,2H,H-1′),1.67(s,3H,-CH 3 ),1.64(s,3H,-CH 3 )；HRMS[ESI]:calcd for C 35 H 32 O 9 Na([M+Na] + ),619.1944；found,619.1934.
the physicochemical properties of compound 28 are as follows:
1) light yellow solid, melting point 115-;
2) the infrared spectrogram, nuclear magnetic resonance spectrogram and high-resolution mass spectrum of the compound are characterized in that:
IR cm -1 (KBr):2929,1718,1586,1500,1225,1090； 1 H NMR(500MHz,CDCl 3 )δ:7.70-7.72(m,2H,Ar-H),7.53-7.55(m,2H,Ar-H),7.15(d,J＝8.5Hz,1H,Ar-H),6.93(d,J＝8.5Hz,1H,Ar-H),6.85(d,J＝8.0Hz,1H,Ar-H),6.78(t,J＝8.5Hz,1H,Ar-H),6.50(d,J＝11.5Hz,1H,H-4),5.79-5.84(m,1H,H-3),5.09(t,J＝6.5Hz,1H,H-2′),4.92(d,J＝6.5Hz,2H,H-2),4.25-4.34(m,8H,-OCH 2 CH 2 O-),3.85(s,3H,-OCH 3 ),3.26(s,2H,H-1′),1.59(s,3H,-CH 3 ),1.54(s,3H,-CH 3 )； 13 C NMR(100MHz,CDCl 3 )δ165.92,163.90,157.98,148.35,147.86,147.72,143.27,143.08,131.80,128.21,127.66,126.30,124.20,123.52,123.49,123.28,122.31,122.20,121.73,119.65,119.08,117.33,117.04,108.08,64.69,64.62,64.07,61.96,55.84,25.70,23.45,17.78；HRMS[ESI]:calcd for C 33 H 32 O 9 Na([M+Na] + ),595.1944；found,595.1933.
the physicochemical properties of compound 29 are as follows:
1) light yellow solid, melting point 66-68 deg.C, yield 26%;
2) the infrared spectrogram, nuclear magnetic resonance spectrogram and high-resolution mass spectrum of the compound are characterized in that:
IR cm -1 (KBr):2926,1714,1632,1503,1284,1125； 1 H NMR(500MHz,CDCl 3 )δ:7.73(d,J＝15.5Hz,1H,-CH＝CH-),7.54(d,J＝15.5Hz,1H,-CH＝CH-),6.99-7.13(m,5H,Ar-H and H-5),6.77-6.88(m,3H,Ar-H and H-6),6.45-6.52(m,2H,-CH＝CH-and H-4),6.25(d,J＝16.0Hz,1H,-CH＝CH-),5.80-5.85(m,1H,H-3),5.11(t,J＝5.5Hz,1H,H-2′),4.84(d,J＝6.0Hz,2H,H-2),4.26-4.28(m,8H,-OCH 2 CH 2 O-),3.84(s,3H,-OCH 3 ),3.26(s,2H,H-1′),1.67(s,3H,-CH 3 ),1.63(s,3H,-CH 3 )； 13 C NMR(100MHz,CDCl 3 )δ167.01,164.93,157.95,147.65,146.29,146.02,145.61,144.49,143.75,143.64,131.79,128.20,128.09,127.80,127.68,126.28,123.17,122.35,122.08,122.04,121.73,117.81,117.64,116.97,116.74,116.07,114.79,108.03,64.58,64.54,64.19,61.66,55.81,25.77,23.45,17.88；HRMS[ESI]:calcd for C 37 H 36 O 9 Na([M+Na] + ),647.2257；found,647.2240.
the physicochemical properties of compound 30 are as follows:
1) light yellow liquid, yield 47%;
2) the infrared spectrogram, nuclear magnetic resonance spectrogram and high-resolution mass spectrum of the compound are characterized in that:
IR cm -1 (KBr):2922,1732,1597,1274,1097； 1 H NMR(500MHz,CDCl 3 )δ:9.39(s,1H,Ar-H),9.21(s,1H,Ar-H),8.85(d,J＝4.5Hz,1H,Ar-H),8.77-8.78(m,1H,Ar-H),8.43-8.45(m,1H,Ar-H),8.26-8.29(m,1H,Ar-H),7.44-7.48(m,1H,Ar-H),7.37-7.40(m,1H,Ar-H),7.16(d,J＝8.5Hz,1H,H-5),6.84(d,J＝8.5Hz,1H,H-6),6.55(d,J＝11.5Hz,1H,H-4),5.84-5.89(m,1H,H-3),5.07(t,J＝6.5Hz,1H,H-2′),5.00(d,J＝6.5Hz,2H,H-2),3.87(s,3H,-OCH 3 ),3.29(s,2H,H-1′),1.57(s,3H,-CH 3 ),1.50(s,3H,-CH 3 )；HRMS[ESI]:calcd for C 27 H 26 N 2 O 5 Na([M+Na] + ),481.1739；found,481.1735.
the physicochemical properties of compound 31 are as follows:
1) light yellow liquid, yield 24%;
2) the infrared spectrogram, nuclear magnetic resonance spectrogram and high-resolution mass spectrum of the compound are characterized in that:
IR cm -1 (KBr):2922,1737,1606,12741,1103； 1 H NMR(500MHz,CDCl 3 )δ:8.85(d,J＝5.5Hz,2H,Ar-H),8.76(d,J＝5.5Hz,2H,Ar-H),7.98-7.99(m,2H,Ar-H),7.81-7.82(m,2H,Ar-H),7.15(d,J＝8.5Hz,1H,H-5),6.83(d,J＝8.5Hz,1H,H-6),6.52(d,J＝11.5Hz,1H,H-4),5.83-5.88(m,1H,H-3),5.05(t,J＝7.0Hz,1H,H-2′),4.99(d,J＝6.5Hz,2H,H-2),3.87(s,3H,-OCH 3 ),3.27(s,2H,H-1′),1.56(s,3H,-CH 3 ),1.49(s,3H,-CH 3 )；HRMS[ESI]:calcd for C 27 H 26 N 2 O 5 Na([M+Na] + ),481.1739；found,481.1731.
the physicochemical properties of compound 32 are as follows:
1) red solid, melting point 152-;
2) the infrared spectrogram, nuclear magnetic resonance spectrogram and high-resolution mass spectrum of the compound are characterized in that:
IR cm -1 (KBr):3099,2917,1718,1605,1267,1104,490； 1 H NMR(500MHz,CDCl 3 )δ:7.21(d,J＝8.5Hz,1H,H-5),6.80(d,J＝8.5Hz,1H,H-6),6.66(d,J＝11.5Hz,1H,H-4),5.89-5.94(m,1H,H-3),5.14(t,J＝7.0Hz,1H,H-2′),4.95(s,2H,Ferrocene-H),4.90(d,J＝6.0Hz,2H,H-2),4.83(s,2H,Ferrocene-H),4.49(s,2H,Ferrocene-H),4.39(s,2H,Ferrocene-H),4.33(s,5H,Ferrocene-H),4.20(s,5H,Ferrocene-H),3.86(s,3H,-OCH 3 ),3.29(s,2H,H-1′),1.63(s,6H,-CH 3 )； 13 C NMR(100MHz,CDCl 3 )δ:171.60,169.63,158.10,147.85,131.96,128.68,127.65,126.52,123.45,122.30,121.86,108.00,71.59,71.37,71.09,70.64,70.51,70.24,69.90,69.83,61.35,55.85,25.75,23.51,17.91；HRMS[ESI]:calcd for C 37 H 36 Fe 2 O 5 Na([M+Na] + ),695.1159；found,695.1143.
example 2: tetranychus cinnabarinus bioassay experiment:
1. the test insects: tetranychus cinnabarinus (Bois) was bred by passage in this laboratory. Agricultural pest mites have the characteristics of small size, quick propagation, strong adaptability, easy generation of drug resistance and the like [ infection Biochemistry and Molecular Biology,2020,120:103347 ], the embodiment takes tetranychus cinnabarinus as a representative, and tetranychus cinnabarinus is the largest group in agricultural pest mites; tetranychus cinnabarinus is a representative harmful mite, which is mainly harmful due to mechanical damage caused by sucking juice on the back of leaves, and is mostly generated in China [ Plant Protection,2005,2:90-91 ].
2. Sample and reagent:
the samples were: 98.32% spirodiclofen technical material (provided by Shaanxi Meibang pesticide Co., Ltd.) (positive control), coumarin a, osthole b, intermediate c, intermediate d and the compounds 1-32 prepared in example 1, acetone (solvent, Chengdu Kelong chemical reagent factory, analytically pure) and water.
3. The bioassay method comprises the following steps: the FAO recommended glass slide immersion method was used:
preparing 0.1% of tween 80 mother liquor: 25mg of Tween 80 was weighed out and dissolved in 5mL of acetone solution, and then dissolved in distilled water to 250mL for use.
Preparing a primary screening liquid medicine: 3.0mg of test compound is weighed respectively, dissolved by 120 microliter of acetone (2 percent of the target volume), and then prepared 0.1 thousandth of Tween 80 is added to the solution with constant volume of 6.0mL, namely 500mg/L solution is prepared for preliminary screening.
Preparing test mites: attaching a double-sided adhesive tape with the width of 1cm to one end of a glass slide, selecting healthy and active female tetranychus cinnabarinus with the same mite age by using a No. 0 writing brush, carefully and orderly adhering the back of the female tetranychus cinnabarinus to the double-sided adhesive, adhering about 35 heads of each glass slide to form 2 rows, placing the glass slide adhered with the tested mites in an iron plate padded with a moist sponge, placing the iron plate in a light incubator under the conditions of 26 +/-1 ℃, relative humidity of 60-80% and light L: D of 14 h: 10h, placing for 4h, checking by using a stereomicroscope, removing dead and inactive individuals, and recording the number of live mites on each glass slide.
Soaking the medicine: the end of the glass slide with the mites is shaken and soaked in the test liquid medicine for 5s, then taken out, a small filter paper strip is carefully used for sucking off the redundant liquid medicine (the mites cannot be touched) and then placed back to an iron plate, the glass slide is placed in a light culture box under the same feeding condition, one glass slide is treated, each treatment is repeated for 3 times, and 0.1 per thousand Tween 80 solution is used as a blank control.
Counting results: after the medicine is soaked for 24 hours, taking out the slide, examining the result under a stereomicroscope, lightly touching the mite body with the tip of a writing brush during examination, taking the dead person as the dead person, and recording the number of dead individuals; the observation was continuously recorded for 72 hours.
TABLE 1 acaricidal Activity of coumarins, osthole, intermediates c, d and derivatives 1-32 thereof of the present invention
Figure BDA0002927594940000191
Figure BDA0002927594940000201
And (4) conclusion:
the result shows that the acaricidal activity of the partial coumarin compound ester derivative for 72 hours is remarkably improved compared with that of coumarin and osthole, and the acaricidal activity of the partial derivative (19-24) for 72 hours is equivalent to that of spirodiclofen, so that the partial derivative is expected to be used for preparing efficient, environment-friendly and low-toxicity plant source acaricides.
Example 3: mythimna separata growth test
1. Test insects: the 3 rd-instar early oriental armyworm (Mythimna separata Walker) is provided by the pollution-free pesticide research center of northwest agriculture and forestry science and technology university. The present example is represented by oriental armyworm, which is a representative pest of lepidoptera, and has migratory flight, paroxysmal nature, and overeating nature; in a major outbreak, the leaves of the Plant may be completely exposed to light, causing severe crop losses, even in the end of crop harvest [ Plant Protection,2013,39, 117-.
2. Sample and reagent: osthole b, intermediate d, toosendanin (positive control), 5-7,9,11-32 of the compound prepared in example 1, acetone (solvent, chemical reagent factory, analytical pure of medeto).
3. The bioassay method comprises the following steps:
leaflet butterfly addition method (Zhang Xing and Zhao Hao Huan 1983): acetone as a blank control, ChuanToosendanin was used as a drug control to determine the activity of the test compound at a concentration of 1 mg/mL; spreading a layer of filter paper on the bottom of a glass culture dish with the diameter of 9cm, adding water for moisturizing, picking 10-head 3-instar prophase larvae per dish, and repeating three times for each sample treated. Removing main veins from newly-picked oat leaves, and cutting into 1 × 1cm 2 Soaking the small butterfly in the prepared liquid medicine to be detected and the reference liquid medicine for 3s, naturally airing, and feeding the test insects; breeding under the conditions of room temperature of about 25 ℃, humidity of 35-80% and illumination time of 12h/12 h. After the test insects eat the oat leaves, adding the leafbutterfly with the liquid medicine, and feeding the fresh leaves without the liquid medicine after feeding for 48 hours until the feathering. Regularly recording the feed intake, the number of live mouths, the expression symptoms and the like of the test insects; the results of the test were obtained and the corrected mortality (%) of the test insects at different stages was calculated according to the following formula.
Figure BDA0002927594940000211
TABLE 2 Activity of 5-7,9,11-32 ester derivatives of coumarins of the present invention against mythimna
Figure BDA0002927594940000212
Figure BDA0002927594940000221
And (4) conclusion:
the results show that the final death rate of partial coumarin ester derivatives (7,9,12,13,16,18,19 and 30) to oriental armyworm is 50.0-64.3%, which is higher than that of commercial toosendanin. The compound of the invention has better growth and development activity on oriental armyworm larvae, so the compound is expected to be used for preparing environment-friendly and low-toxicity botanical insecticides.

Claims (7)

1. The coumarin compound ester derivative is characterized in that the chemical structural formula is shown as the formula (I):
Figure FDA0003682134460000011
the structure of the compound shown in the formula (I) is one of the following structures:
(1):R 1 ＝R 2 ＝H；R 3 ＝-CH 2 CH 2 CH 3 ；
(2):R 1 ＝R 2 ＝H；R 3 ＝-CH 2 (CH 2 ) 8 CH 3 ；
(3):R 1 ＝R 2 ＝H；R 3 ＝-CH 2 (CH 2 ) 9 CH 3 ；
(4):R 1 ＝R 2 ＝H；R 3 ＝-CH 2 (CH 2 ) 11 CH 3 ；
(5):R 1 methoxy; r 2 2-butenyl-3-methyl; r 3 ＝-CH 3 ；
(6):R 1 Methoxy; r 2 2-butenyl-3-methyl; r 3 ＝-CH 2 CH 3 ；
(7):R 1 Methoxy; r 2 2-butenyl-3-methyl; r 3 ＝-CH 2 CH 2 CH 3 ；
(8):R 1 Methoxy; r 2 2-butenyl-3-methyl; r 3 ＝-CH 2 (CH 2 ) 8 CH 3 ；
(9):R 1 Methoxy; r 2 2-butenyl-3-methyl; r 3 ＝-CH 2 (CH 2 ) 9 CH 3 ；
(10):R 1 Methoxy; r 2 2-butenyl-3-methyl; r 3 ＝-CH 2 (CH 2 ) 11 CH 3 ；
(11):R 1 Methoxy; r 2 2-butenyl-3-methyl; r is 3 A phenyl group;
(12):R 1 methoxy;R 2 2-butenyl-3-methyl; r 3 Meta-fluorophenyl;
(13):R 1 methoxy; r 2 2-butenyl-3-methyl; r 3 Para-fluorophenyl;
(14):R 1 methoxy; r 2 2-butenyl-3-methyl; r 3 O-chlorophenyl;
(15):R 1 methoxy; r 2 2-butenyl-3-methyl; r is 3 Meta-chlorophenyl;
(16):R 1 methoxy; r 2 2-butenyl-3-methyl; r 3 Para-chlorophenyl;
(17):R 1 methoxy; r 2 2-butenyl-3-methyl; r 3 Para-bromophenyl;
(18):R 1 methoxy; r 2 2-butenyl-3-methyl; r 3 Meta-trifluoromethylphenyl;
(19):R 1 methoxy; r 2 2-butenyl-3-methyl; r 3 Para-trifluoromethylphenyl;
(20):R 1 methoxy; r 2 2-butenyl-3-methyl; r 3 O-methoxyphenyl;
(21):R 1 methoxy; r 2 2-butenyl-3-methyl; r 3 Meta-methoxyphenyl;
(22):R 1 methoxy; r 2 2-butenyl-3-methyl; r 3 Para-methoxyphenyl;
(23):R 1 methoxy; r 2 2-butenyl-3-methyl; r 3 Para-methylphenyl;
(24):R 1 methoxy; r 2 2-butenyl-3-methyl; r 3 α -naphthylethyl;
(25):R 1 methoxy; r 2 2-butenyl-3-methyl; r is 3 Cinnamyl;
(26):R 1 methoxy; r 2 2-butenyl-3-methyl; r 3 3,4- (methylenedioxy) phenyl;
(27):R 1 methoxy; r 2 2-butenyl-3-methyl; r 3 3,4- (methylenedioxy) cinnamyl;
(28):R 1 methoxy; r 2 2-butenyl-3-methyl; r 3 (ii) 3,4- (ethylenedioxy) phenyl;
(29):R 1 methoxy; r 2 2-butenyl-3-methyl; r 3 3,4- (ethylenedioxy) cinnamyl;
(30):R 1 methoxy; r 2 2-butenyl-3-methyl; r 3 -3-pyridyl;
(31):R 1 (ii) methoxy; r 2 2-butenyl-3-methyl; r 3 4-pyridyl;
(32):R 1 methoxy; r 2 2-butenyl-3-methyl; r 3 Ferrocenyl.
2. The use of the coumarin ester derivative as claimed in claim 1 in the preparation of insecticides.
3. Use of the coumarin ester derivative as claimed in claim 1 in the preparation of acaricides.
4. The process for the preparation of a coumarin compound according to claim 1, wherein the process comprises:
step 1, reacting a coumarin compound with an infrared aluminum solution to prepare an intermediate, wherein the structural formula of the coumarin compound is shown as a formula (II):
Figure FDA0003682134460000021
step 2, intermediate and R 3 COOH to obtain the compound shown in the formula (I), wherein:
(1):R 1 ＝R 2 ＝H；R 3 ＝-CH 2 CH 2 CH 3 ；
(2):R 1 ＝R 2 ＝H；R 3 ＝-CH 2 (CH 2 ) 8 CH 3 ；
(3):R 1 ＝R 2 ＝H；R 3 ＝-CH 2 (CH 2 ) 9 CH 3 ；
(4):R 1 ＝R 2 ＝H；R 3 ＝-CH 2 (CH 2 ) 11 CH 3 ；
(5):R 1 methoxy; r is 2 2-butenyl-3-methyl; r 3 ＝-CH 3 ；
(6):R 1 Methoxy; r 2 2-butenyl-3-methyl; r is 3 ＝-CH 2 CH 3 ；
(7):R 1 Methoxy; r 2 2-butenyl-3-methyl; r 3 ＝-CH 2 CH 2 CH 3 ；
(8):R 1 Methoxy; r 2 2-butenyl-3-methyl; r 3 ＝-CH 2 (CH 2 ) 8 CH 3 ；
(9):R 1 Methoxy; r 2 2-butenyl-3-methyl; r 3 ＝-CH 2 (CH 2 ) 9 CH 3 ；
(10):R 1 Methoxy; r 2 2-butenyl-3-methyl; r 3 ＝-CH 2 (CH 2 ) 11 CH 3 ；
(11):R 1 Methoxy; r 2 2-butenyl-3-methyl; r 3 A phenyl group;
(12):R 1 methoxy; r 2 2-butenyl-3-methyl; r 3 Meta-fluorophenyl;
(13):R 1 methoxy; r 2 2-butenyl-3-methyl; r 3 Para-fluorophenyl;
(14):R 1 methoxy; r 2 2-butenyl-3-methyl; r 3 O-chlorophenyl;
(15):R 1 methoxy; r 2 2-butenyl-3-methyl; r 3 Meta-chlorophenyl;
(16):R 1 methoxy; r 2 2-butenyl-3-methyl; r 3 Para-chlorophenyl;
(17):R 1 methoxy; r 2 2-butenyl-3-methyl; r 3 Para-bromophenyl;
(18):R 1 methoxy; r 2 2-butenyl-3-methyl; r 3 Meta-trifluoromethylphenyl;
(19):R 1 methoxy; r 2 2-butenyl-3-methyl; r 3 Para-trifluoromethylphenyl;
(20):R 1 methoxy; r 2 2-butenyl-3-methyl; r 3 O-methoxyphenyl;
(21):R 1 methoxy; r 2 2-butenyl-3-methyl; r 3 Meta-methoxyphenyl;
(22):R 1 methoxy; r 2 2-butenyl-3-methyl; r 3 Para-methoxyphenyl;
(23):R 1 methoxy; r 2 2-butenyl-3-methyl; r 3 Para-methylphenyl;
(24):R 1 methoxy; r 2 2-butenyl-3-methyl; r 3 α -naphthylethyl;
(25):R 1 methoxy; r 2 2-butenyl-3-methyl; r 3 Cinnamyl;
(26):R 1 methoxy; r 2 2-butenyl-3-methyl; r 3 3,4- (methylenedioxy) phenyl;
(27):R 1 methoxy; r 2 2-butenyl-3-methyl; r 3 3,4- (methylenedioxy) cinnamyl;
(28):R 1 methoxy; r 2 2-butenyl-3-methyl; r 3 (ii) 3,4- (ethylenedioxy) phenyl;
(29):R 1 methoxy; r 2 3-Jia2-butenyl-yl; r 3 3,4- (ethylenedioxy) cinnamyl;
(30):R 1 methoxy; r 2 2-butenyl-3-methyl; r 3 -3-pyridyl;
(31):R 1 methoxy; r 2 2-butenyl-3-methyl; r 3 4-pyridyl;
(32):R 1 methoxy; r 2 2-butenyl-3-methyl; r 3 Ferrocenyl.
5. The method for preparing esters of coumarin compounds according to claim 4, wherein the reaction in step (1) is carried out in tetrahydrofuran solution in the presence of nitrogen gas, and the reaction temperature is-78-10 ℃.
6. The method for preparing esters of coumarins according to claim 4, wherein R is 3 COOH is selected from one of acetic acid, propionic acid, butyric acid, undecanoic acid, lauric acid, tetradecanoic acid, benzoic acid, m-fluorobenzoic acid, p-fluorobenzoic acid, o-chlorobenzoic acid, m-chlorobenzoic acid, p-bromobenzoic acid, m-trifluoromethylbenzoic acid, p-trifluoromethylbenzoic acid, o-methoxybenzoic acid, m-methoxybenzoic acid, p-methylbenzoic acid, alpha naphthylacetic acid, piperic acid, 3,4- (methylenedioxy) cinnamic acid, 2, 3-dihydro-1, 4-benzodioxane-6-carboxylic acid, 1, 4-benzodioxane-6-acrylic acid, nicotinic acid, isonicotinic acid and ferrocenecarboxylic acid.
7. The method for preparing esters of coumarin compounds according to claim 4, wherein the reaction in step (2) is carried out in anhydrous dichloromethane, and EDC and DMAP are added at the same time, and the reaction temperature is 20-30 ℃.
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